The effect of air exposure on palladium–copper composite membranes

It was found that when electrolessly deposited thin Pd and Pd–Cu membranes were exposed to air at temperatures above 350 °C, their H₂ flux increased substantially immediately after the air exposure, then decreased to a new steady-state value. While this was a quasi-reversible change for the H₂ flux, the flux of insoluble species, such as N₂, irreversibly increased with every air exposure but by a much smaller extent. The extent of these changes was found to be dependent on the exposure time and the temperature of the tests. Thus, we decided to investigate the effect of gas exposures on the properties of these materials.

Palladium and palladium–copper films, prepared by electroless deposition on ceramic supports, and commercial foils were exposed to air, hydrogen and helium at 500 and 900 °C for times varying from 1 h to 1 week with the objective of determining the effect of the different exposure conditions on the surface morphology, the flux of different penetrants and the crystalline structure of the materials. Atomic force microscopy (AFM) and X-ray diffraction (XRD) were used to study the changes occurring in the films under those conditions.

It was observed that the exposure of both the electroless films and the foils to hydrogen and air markedly modified their surface morphology. The hydrogen exposure tended to smooth the surface features whereas the oxygen exposure created new surface features such holes and large peaks. Additionally it was found that the air exposure produced some oxidation of the film to create PdO.

These results suggested that a common hypothesis stating that air oxidation just cleans the surface of the membrane might not be sufficient to explain all of those changes. A contributing effect of air exposure may be the increase in surface area due to the formation of palladium oxide. However, the extent of the surface area increase was insufficient to explain the increase in steady-state H₂ flux.